Synthesis of glycose hydrocarbon sulfonate surfactants

ABSTRACT

Glycose hydrocarbonsulfonates useful as surfactants are prepared by reacting a glycose with a hydrocarbonsulfonyl halide in the presence of a tertiary amine.

United States Patent 1111 3,622,564

[72] Inventors Edmund T. Kittleman; [56] ReierencesCiled E 3 1969 3,057,855 10/1962 Smithetal 260/234 [45] Patented 197 3,070,595 12/1962 Petraceketal..... 260/234 2,786,833 3/1957 Wurzburgetal. 260/234 [73] Assignee Phillips Petroleum Company Primary Examiner-Lewis Gotts Assistant Examiner-Johnnie R. Brown SYNTHESIS OF GLYCOSE HYDROCARBON Atlomey-Pendleton, Neuman, Williams & Anderson SULFONATE SURFACTANTS l 1 Claims, No Drawings ABSTRACT: Glycose hydrocarbonsulfonates useful as surfac- [52] US. Cl. 260/234 R, [ants are prepared byvreacfing a glycose with a hydrocarbon 252/353 0 s1 1 1m. 01 C07C 69/32 halde [50] Field of 260/234, 234 R SYNTHESIS OF GLYCOSE HYDROCARBON SULFONATE SURFACTANTS This invention relates to the synthesis of glycose hydrocarbonsulfonates which are useful as surfactants.

The copending Pat. application, Ser. No. 788,958 filed Jan. 3, 1969 by Roy A. Gray, Edmund T. Kittleman and Gardner C. Ray, discloses novel glycose hydrocarbonsulfonates which possess surface active properties rendering them useful in detergent and other applications. As disclosed in that application, the glycose hydrocarbonsulfonates are prepared in two steps; in step one, an alkali metal salt of a glycose is formed and then in step two the alkali metal glycate is reacted with a hydrocarbonsulfonyl halide to fonn a desired glycose hydrocarbonsulfonate.

We have found that glycoses can be reacted directly with hydrocarbonsulfonyl halides to form the glycose hydrocarbon- .sulfonates without the necessity of first forming an alkali metal glycate. This discovery, forming the basis of this invention, affords numerous advantages among which can be mentioned: fewer process steps, reduction in equipment and reduction in reactant costs.

The improved process of the invention comprises reacting a glycose with a hydrocarbonsulfonyl halide in the presence of a tertiary amine.

The process of the present invention can be represented as follows:

wherein X is chlorine, bromine or iodine,

n is an integer of from one to 12 inclusive, preferably one to six inclusive, and

R is alkyl or cycloalkyl having from about six to 25 carbon atoms inclusive, preferably 12 to 18 carbon atoms inclusive, such as hexyl, octyl, isooctyl, pentacosyl, decyl, dodecyl, tetradecyl, hexadecyl, cyclododecyl, octadecyl, nonadecyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentacosyl, cyclooctadecyl, cyclononyl, cyclodecyl and the like.

The representation [(G)(OH),,] represents a glycose molecule and the (Old),. groups thereof can be any of the ac tive hydroxyl groups in the molecule.

The preferred hydrocarbonsulfonyl halides to employ in the process of this invention are straight chain l-alkanesulfonyl halides in which the alkane moiety contains from 12 to 18 carbon atoms inclusive.

The tertiary amine employed in the synthesis method of this invention can be any amine wherein nitrogen is bonded to three carbon atoms and containing from three to 12 carbon atoms inclusive. The amines can contain one or more nitrogen atoms. Representative amines which can be employed thus include trimethylamine, tri-n-butylamine, triethylamine, N- methylpiperidine, N,N,N',N'-tetramethylethylenediamine,

. N,N'-diethylpiperazine, and the like.

The process of this invention is conducted by mixing a glycose with a hydrocarbonsulfonyl halide at a temperature in the range of about -l to 25 C. under pressure suificient to maintain the reactants substantially completely in the liquid phase. The reaction is preferably accomplished under substantially anhydrous conditions. Moreover, if desired, suitable diluents can be employed in amounts as high as 95 weight percent of the reaction medium. Examples of suitable diluents include N,N-dimethylformamide, N,N-diethylacetamide, tetrahydrofuran, tetrahydropyran, N-methylpyrrolidone, and the like. The diluent employed should be substantially nonreactive under the reaction environment. The reaction is generally complete in periods ranging from about minutes to about 48 hours.

It is essential to the process of this invention that a tertiary amine be present. The tertiary amines are preferably employed in amounts of about 0.1 to moles per mole of glycose present, inclusive.

The hydrocarbonsulfonyl halides which are employed according to this invention can be synthesized by any convenient means. For example, such compounds can be prepared in accordance with the teachings of U5. Pat No. 3,238,255 which relates to sulfochlorination of hydrocarbons. Likewise, a terminal olefin of suitable nature can be reacted with thiolacetic acid followed by hydrolysis to yield the respective terminal thiol which can subsequently be halogenated in the presence of water to yield the l-alkanesulfonyl halide desired. Suitable means of effecting these syntheses are disclosed by L. Bateman ct al., J. Chem. Soc, 2838 (1958) and Douglass and JohnsonJ. Am. Chem. $00., 60, 1486 (1938). in the practice of the process of the invention the hydrocarbonsulfonyl halides are generally employed in amounts of from about 0.1 to about 10 moles per mole-of glycose.

The glycoses which can be employed in accordance with 'this invention include mono and polysaccharides, having in the range of l to about 5 monosaccharide units. Each saccharide unit can contain in the range of about four to about seven carbon atoms, and can be either an aldose or a ketose unit. Representative examples of suitable glycoses are sucrose, fructose, sorbose, glucose, maltose, mannose, galactose, threose, xylose, arabinulose, lactose, ratfinose, stachyose, and the like. Glycoses of this group which are nonreducing sugars are preferred and nonreducing disaccharides, such as sucrose, are particularly preferred.

The invention is further illustrated by the following examples.

EXAMPLE I l-lexadecane is sulfochlorinated with chlorine and sulfur dioxide, promoted by ultraviolet light, according to the process of US. Pat. No. 3,238,255. The resultant product, which is separated by fractional crystallization, is found to be comprised largely of hexadecanesulfonyl chloride.

A milliliter quantity of 0.5 M sucrose in dimethylformamide (50 moles of sucrose) is charged to a stirred reactor with 2.8 milliliters (20 moles) of triethylamine. A total of 10 moles of hexadecanesulfonyl chloride, prepared as above, is then slowly added over a period of about 45 minutes. The mixture is cooled to about l0 to 0 C. for 60 additional minutes. The reaction mixture is then added to 2l0 milliliters of toluene. Unreacted sucrose and triethylamine hydrochloride precipitates, the mixture is filtered, and the filtrate added to 128 milliliters of heptane. A lower phase of about 20 milliliters separates, and is taken up in a solution comprised of 1:2 methanolzisopropanol (v/v). The upper phase is further diluted with 282 milliliters of heptane, and the bottom phase which separates is taken up in 100 milliliters of methanol. The two alcoholic extracts are combined and stripped to a colorless oil, The residual oil is mixed with 500 milliliters of heptane and 100 milliliters of chloroform. Upon vigorous agitation, a precipitate fOlITlS. The precipitate is separated and dissolved in a mixture comprised of chloroform and heptane in a 2:1 v/v ratio. The residue is dried in vacuo over P 0 The resulting sucrose hexadecanesulfonate product weighs 5.8 grams. Elemental composition for sucrose hexadecanesulfonate is calculated to be: C, 53.3 percent; H, 8.6 percent; S, 5.] percent. Elemental composition of the sucrose hexadecanesulfonate product formed is detennined to be: C, 48.6 percent; H, 7.9 percent; S, 4.2 percent.

EXAMPLE ll Following the procedure of example I, mannose is reacted, in the presence of N-methylpiperidine, with nonanesulfonyl chloride to form as product, mannose nonanesulfonate.

EXAMPLE [I] Following the procedure of example I, maltose is reacted, in the presence of N,N'-diethylpiperazine (0.5 mole per mole of maltose), with tridecanesulfonyl bromide to form as product, maltose tridecanesulfonate.

EXAMPLE IV A. l-Dodecanethiol is prepared by a method employed by L. Bateman et al., J. Chem. 800., 2838 (1958) [cf. Brown et al., ibid., 2123 (1951)], the reaction being represented as fol- 5 lows:

A KOH-i-HO Elemental Analyses kc EH 555 Found for Product 71.3 12.9 15.4 Calculated for c,,n,,s 71.3 [2.9 15.8

wherein R represents the dodecyl group.

EXAMPLE V EXAMPLE VI A 100 milliliter portion of 0.5 M sucrose in dimethylformamide moles of sucrose) is charged to a stirred reactor with 50 2 grams (20 moles) of triethylamine. Upon cooling of the reactor contents to about -10 C., a solution comprised of 3.25 grams (10 moles) of l-tetradecanesulfonyl chloride (prepared as in example V) in 25 milliliters of toluene is slowly added over a 50 minute period. Stirring is continued at about l0 C. for an additional minutes. The reaction mixture is then diluted with 185 milliliters of toluene to precipitate sucrose and triethylamine hydrochloride. The supematant liquid is separated and subsequently diluted with 60 1 140 milliliters of n-heptane. Phases fonn. The lower phase is separated and stripped of volatiles to leave an oil. This oil is contacted with a mixture comprised of 200 milliliters of nheptane and 40 milliliters chloroform. An amorphous solid precipitates. The supernatant liquid is decanted, and the residue is stripped of volatiles to leave an amorphous solid prior in drying in vacuo over P 0 to give 6.4 grams of sucrose l-tetradecanesulfonate product. Elemental composition of this product is determined and found to be in agreement with the elemental composition calculated for a sucrose 1- tetradecanesulfonate thus:

nc 9m k5 Found 49.2 8.1 4.: Calculated 51.8 8.3 5.3 75

EXAMPLE VII Following the procedure of example VI, sucrose is reacted with l-dodecanesulfonyl chloride prepared as in example IV.

The resulting product, sucrose l-dodecanesulfonate, has elemental analyses as follows:

Elemental Analyses Found 48.6 7.9 4.5

Calculated 50.2 8.0 5.6

EXAMPLE Vlll [n a manner similar to example VI, sucrose is reacted with l-hexadecanesulfonyl chloride prepared as in example V. The resulting product, sucrose 1-hexadecanesulfonate, has elemental analyses as follows:

Elemental Analyses %C EH 58 Found 52.0 8.7 4.5 Calculated 53.3 8.7 5. l

EXAMPLE [X In a manner similar to example Vl, sucrose is reacted with 7-tetradecanesulfonyl chloride prepared as in example V. The resulting product, sucrose 7-tetradecanesulfonate, has elemental analyses as follows:

Elemental Analyses %C H as Found 51.4 8.5 4.4 Calculated 51.8 8.3 5.3

EXAMPLE X In a manner similar to example Vl, sucrose is reacted with l-octadecanesulfonyl chloride prepared as in example V. The resulting product, sucrose l-octadecanesulfonate, has elemental analyses as follows:

Elemental Analyses %C %H %S Found 50.9 8.3 3.7

Calculated 54.6 8.8 4.9

The glycose hydrocarbonsulfonates produced in accordance with this invention are surfactants useful as detergents. Representative glycose sulfonates produced by the process of this invention were evaluated as detergents by washing standard soiled cotton cloth (UST is U.S. Testing Company cloth; TF is Testfabric Company cloth) in a Tergotometer and then measuring the difference in light reflectance between washed and unwashed cloth by means of a MultiPurpose Reflectometer. The detergency ratings which follow in table 1 are defined by the relationship: (lR) (lR) wherein (IR) represents the increase in reflectance obtained in the presence of the active detergent species plus test additives (defined below) and (IR), denotes increase in reflectance effected by the additives alone. For example, formulations were prepared by dissolving 0.6 gram active ingredient and 2.4 grams test additives (stock solution aliquot) in sufficient water to give 2 liters of solution. In table 1, below, the detergency rating at this concentration level is indicated in the 0.15 percent column results based on lower concentration levels are listed in the columns labeled 0.10 percent and 0.05 percent, and are determined in an analogous manner. Test additives which constituted 80 percent of the formulation consisted of sodium tripolyphosphate (50 percent), sodium sulfate (15 percent), sodium metasilicate (5 percent), carboxymethyl cellulose (0.8 percent) and water (9.2 percent) by weight. The other 20 percent by weight of the formulation was in each case made up of the active ingredient, i.e., the prospective surfactant to be tested. (IR), values for UST and TF cloths at concentrations of 0.15 percent, 0.10 percent and 0.05 percent were, respec- 4. The process of claim 1 wherein there is employed a hydrocarbonsulfonyl halide wherein the hydrocarbon moiety is an alkyl or cycloalkyl radical containing from six to 25 carbon atoms.

tively: 8.2, 10.2; 7.4,9.6; and 7.4, 9.6. 5 5. The process of claim 1 wherein there is employed a TABLE 1 Surfactant UST 'IF UST TF UST 'IF Sucrose l-tetradecanesultonates 4.5 3. 9 5. 6 3. 8 4.4 4.3 Sucrose 7-tetradecanesultonates 3.3 3.0 1.8 2. 7 0.3 1. 6 Sucrose l-hexadecanesulfonates 5.7 3.7 5.1 4.8 4. 6 3.2 Sucrose l-dodecanesulionates 4.1 3.1 4.0 3. 2 1.4 2. 5 ucrose l-octadecanesulionates 4.6 4.0 4.7 3. s 3.7 2. s

The data of table 1 show that the hydrocarbonsull5 hydrocarbonsulfonyl halide wherein the hydrocarbon moiety fonates produced by the process of this invention are useful as is an alkyl or cycloalkyl radical containing from 12 to l8' carsurfactants in detergents. The glycose sulfonates are bon atoms. biodegradable under both aerobic and anaerobic conditions. 6. The process of claim 1 wherein there is employed a Those modifications and equivalents which fall within the hydrocarbonsulfonyl halide wherein the hydrocarbon moiety spirit of the invention are to be considered a part thereof. is a straight chain alkyl radical containing from 12 to 18 car- We claim: bon atoms.

1. A process for producing glycose hydrocarbonsulfonates 7. The process of claim 1 wherein the hydrocarbonsulfonate which comprises reacting a glycose with a hydrocarbonsulfoemployed is a l-alkanesulfonyl halide with the alkane moiety nyl halide, the reaction being carried out under substantially containing from 12 to 18 carbon atoms. anhydrous conditions at a temperature not substantially in ex- 8. The proc ss of cl im 1 herein a nonredueing glycose is cess of 25 C. in the presence of an amine containing from mploy three to l2 carbon atoms in the molecule and wherein the The Process of claim 1 wherein the gly se employed is nitrogen is bonded to threecarbon atoms. sucrose.

2. The process of claim 1 carried out at a temperature in the 10. A process in accordance with claim 7 wherein a nonrange of from -10 to 25 C. reducing glycose is employed.

3. The process of claim 1 carried out in the presence of a 11. A process in accordance with claim 7 wherein the nonreactive diluent. glycose employed is sucrose.

Patent No. 3 622.564

Inventor(s) Column 2, line 39,

line

line

(SEAL) At'uest:

EDWARD ILFLETCHFZRJR. Attesting Officer UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Date November 23, 1971 Edmund T. Kittleman and ROY A. Gray 'moles" should be mmoles "in", first occurrence,

"905.3" should be 5.3

Signed and sealed this 16th day of May 1972.

ROBERT GOTTSCHALK It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

40, "moles", both occurrences, should be be to Commissioner of Patents 'ORM PC3-1050 (10-69) USCOMM-DC 60376-P69 Q U.5. GOVERNMENT PRINTNG OFFICE 1 I969 0-36533. 

2. The process of claim 1 carried out at a temperature in the range of from -10* to 25* C.
 3. The process of claim 1 carried out in the presence of a nonreactive diluent.
 4. The process of claim 1 wherein there is employed a hydrocarbonsulfonyl halide wherein the hydrocarbon moiety is an alkyl or cycloalkyl radical containing from six to 25 carbon atoms.
 5. The process of claim 1 wherein there is employed a hydrocarbonsulfonyl halide wherein the hydrocarbon moiety is an alkyl or cycloalkyl radical containing from 12 to 18 carbon atoms.
 6. The process of claim 1 wherein there is employed a hydrocarbonsulfonyl halide wherein the hydrocarbon moiety is a straight chain alkyl radical containing from 12 to 18 carbon atoms.
 7. The process of claim 1 wherein the hydrocarbonsulfonate employed is a 1-alkanesulfonyl halide with the alkane moiety containing from 12 to 18 carbon atoms.
 8. The process of claim 1 wherein a nonreducing glycose is employed.
 9. The process of claim 1 wherein the glycose employed is sucrose.
 10. A process in accordance with claim 7 wherein a nonreducing glycose is employed.
 11. A process in accordance with claim 7 wherein the glycose employed is sucrose. 